Method of treating pine oleo-resins and products resulting therefrom



Dec. 20, 1938.

' METHOD oF 'T'REATINCT PINE OLEO-RESINS AND PRODUCTS RESULTINGTHEREEROM MCG. CLINE Filed Sept. 15, 1937 vPatented Dee. 2o, 1938 y2,140,514 METHOD oF TREATING PINE OLEO-RESINS AND PRODUCTS FROMRESULTING THERE- McGarvey Cline, Jacksonville, ll'la. Applicationseptember 15,1931, serial No. 164,085

28 Claims.

invention relates also to' new stable forms of oleo-Y resinresultantofgsuchrmethods ande-suitable for bulk shipment and lstorage prior toutilization by consuming industries.

Crude pine oleo-resins are the exudates of living pine trees which areproduced by the periodic lo scariflcation of the trees. The exudatesflow from the severed resin ducts of the tree over the scarified face ofthe tree until they are directed by gutters, inserted in the trees, intocups placed on the tree for the collection of such exudates.

The oleo-resin is periodically transferred from u the cups into barrels.

Crude oleo-resin collected from pine trees is a heterogeneous mixture ofmaterials containing primarily a mixture of crystalline resin aci-ds zoand a viscous liquid solution of various materials such as terpenes,resin acids, substances generally termed resines, and other organicconstituents produced in the plant synthesis of the material. Thisprimary mixture is contaminated with many 25 extraneous substances, aswell as with modified oleo-resinous materials. The viscous liquidoleoresinous aggregate is particularly subject to modification duringthe period of time it is exposed in flowing from the scar on the tree tothe cups 30 placed for the collection of the exudate. The flowprogresses in the form of a slow` moving film exposed to atmosphericoxidation and evaporation. The tacky surface of the film facilitates theaccumulation of extraneous impurities by 35. the exudate. Generallyspeaking the crystallized resin acids, associated with the viscousliquid oleo-resinous aggregate, are of relatively high purity, most o1the non crystalline resines, oxidized terpenes, and oxidized resin acidsbeing 40 distributed in the liquid aggregate. The general nature of thematerial treated by the process to be described below may be best shownby a more complete analysis of the component parts of the crude pineoleo-resin aggregate, especially those parts of the aggregate which maybe classified as impurities, as follows:

1. Nonresinous organic materials which become associated with theoleoaresin during its synthesis in the tree.

a. Certain unidentified hydrocarbons. Some of these which are soluble inwater have been separated and some of their general characteristics havebeen determined. One of these characteristics which is pertinent is thatthese hydrocarbons darken in color when heated. Their (Cl. 26o-107)presence in gum rosins is at least partially responsible for colorchanges which occur when gum rosins are subjected to various heatingoperations or to various chemical reactions especially reactionsinvolving the use oi' alkalies in which dark red and yellow coloringmaterials are produced.

b. Small amounts of water derived from the organic saps of the tree.`This water is intimately associated with the oleo-resin, apparently loin solution with portions of the crude aggregate, since its presence isnot obvious from visual inspection. 'I'he organic acids mentioned inparagraph c, below, as well as some of the materials mentioned inparagraph a, are probably associ- 15 ated with this water and may effectits miscibility with the oleo-resin material.

c. Organic acids which are soluble in water and which are volatilewithin the temperature range usually employed in the distillation ofpine oleoresins. These acids are soluble in the oleo-resinous aggregateand also in the terpenes after they are separated from the oleo-resin.'I'hese acids consist largely of acetic and formic acids. 'Iheirpresence in crude oleo-resin is the basis of the corrosive action ofcrude oleo-resin in contact with various metals. Their presence in gumturpentine causes discoloration of commercial turpentine when placed invarious metal containers.

l2. Metallic salts of acetic and formic acids. 30 Metal gutters andmetal cups made of galvanized iron are quite generally used for thecollection of crude oleo-resin., The corrosive action of crudeoleo-resin on these metals results in the formation acetates andformates. The iron salts of these acids are a common cause of .color ingum rosins, especially in the lower grades of gum rosin. These salts arehighly soluble in water but the present practice of processing crudeoleoresin does not remove them prior to distillation so that they remainin the rosin'as an undesirable impurity.

3. Modified terpenes and resin acids produced during the period ofexposure to which the oleoresins are subjected in owing from the resinducts of the tree to the cup placed on the tree for its collection. Bothterpenes and resin acids are unsaturated compounds which oxidize atatmospheric temperatures. The conditions of exposure in a slowly movingfilm are highly favorable to such oxidation. 'I'hese oxidiz'edoleoresinous materials are largely responsible for the different colors.in commercially graded gum rosins and are also responsible for much ofthe discoloration of products derived from various methods rials andlesser degrees of oxidation do not result in compounds which are asinsoluble as the more highly oxidized forms. The general tendency ofoxidation, however, is to lessen solubility and increase the specificgravity, also to darken the color. l

4.1 Dust, pollens and various other finely divided foreign matter whichare practically held in coll loidal suspension in melted oleo-resins.The conditions of thin nlm exposure and the tacky properties ofoleo-resin are exceedingly favorable for the collection of suchimpurities.

5. Chips of wood and bark, flne'sand, pine needles and various othersolids which from various reasons get in the cups and become mixed withthe oleo-resin as it collects.

v6. Rainwater, much of which entering the cups flows over ythe bark ofthe tree. Such water may l contain tannates `and. other vegetableextracts. This water does not mix in any intimate way with theoleo-resin, but some oi' it becomes involved with the viscous materialin the form of drops and larger pockets. The amount of such water whichmay be present in crude oleo-resin varies greatly according to theweather conditions .immediately preceding the collection of the gum fromthe cups, and with the care exercised in the collection of the gum.Crude oleo-resin sinks in water and adheres to the bottom and sides ofthe cups so that extraneous water in the cups may be poured out beforethe gum is placed in a larger receptacle. With ordinary care used incollection such water should not exceed approximately 8% of the totalweight of the material collected.

One object of the present invention is to provide a practical,commercial process for efficiently removing from crude Oleo-resins,impurities including any or all of those mentioned above.

A Vfurther object is to provide a process according to which impuritiesare removedl from crude oleo-resins and whereby the purled material isobtained in a condition which renders it highly satisfactory forshipment or storage and for subsequent use. The use of wooden containersmay be dispensed with, and instead metal containers may be employedwithout danger of corrosion, or of discoloration of the exudates.

A still further object is to provide a process which rendersoleo-resinous material more highly desirable for conversion into highgrade rosin and turpentine.

Another object is to provide a process of purifying and iractionatingoleo-resins.

Another object is to provide an oleo-resin product having highlydesirable characteristics.

The problem of removing the materials of groups 1 and 2 above isdistinctly different from the problem of separating the material ofgroup 6, above. Rain water with its associated impurities-is not asintimately associated with the oleoresinous material and its removal maybe efi'ectively accomplished by various means adaptable to securing agravity sedimentation of this water from the oleo-resinous aggregate. Bythe process oi the present invention, the sedimentation of this waterand other impurities may be accelerated. The removal of water-solubleconstituents of the crude oleo-resin describedin groups 1 and 2 isherein accomplishedby rst establishing a condition favorable todiffusion of these water-soluble materials from the oleo-resinousmaterial lwith which they are intimately Vassoa elated to an aqueoussolvent for them. Then,

after diflusion takes place the aqueous solution is 'removed by gravitysedimentation or other suitsolvents such as additional terpenes or otherthinning agents. It is an object of my invention to further inhibit theformation of solutions by emulsifying the oleo-resin aggregatesimultaneously with the operation of securing iluidity by heat or othermeans. An aqueousmedium is used for the production of emulsions and forproviding a fluid in which the emulsionsnmay be kept suspended fordesired periods of time. so that the aqueoussuspension medium may act asa selective solvent for dissolving water-soluble materials contained inthe crude oleo-resin.

By excessive temperatures, referred to above, I mean temperatures higherthan the boiling point ofthe aqueous phase of the emulsion. (The boilingpoint of the oleo-resin emulsions is about 195 F. at atmosphericpressure.) Such excessive temperatures are avoided because they breakthe emulsions.

Water-soluble impurities are, as indicated above, removed by means of aselective solvent for them applied to the oleo-resinous material underconditions of intimate contact which permits diffusion of thewater-soluble materials from the oleo-resinous material into theselective sol` vent; such diffusion being followed by a substantialseparation of the selective solvent from the oleo-resinous material.

Intimate contact between agents employed in the present process andcrude oleo-resins is obtained by emulsication as for instance with waterand with various aqueous solutions. Emulsication may also, ii. desired,be combined withthe use of solvents; solution and emulsication beingpreferably carried on simultaneously or in close sequence to each other.Crude oleo-resin aggregates may be converted from a viscous into ahighly uid state without converting the aggregates into substantiallyhomogeneous solutions. Instead of being a solution a fluid aggregate maybe a mixture of emulsiiied oleo-resinous materials suspended in or mixedwith a surplus'of an aqueous medium. Whensuch emulsiiied aggregates aresubjected to a period of sedimentation, the various classes of emulsionscomposing the aggregate substantially separate into layers superimposedon each other according to the specic gravities of the minute globulescomposing the emulsion. This separation may be accomplished Withoutsolution of one class of oleoresinous material in other classes; theprocess of solution being limited to that which occurs prior toemulsification. l

Aqueous emulsions of pine oleo-resin may be formed which are highlystable compositions of sions vare so stable that they can be heated totemperatures below the boiling point of the aqueous emulsifying mediumwithout breaking4 the emulsion. They are readily broken, however, by

boiling such as occurs in a process of distillation, which process maybe ultimately used to accompllsh the separation of the emulsiiiedoleo-resins into rosin and turpentine.

Stable emulsions oi' pine oleo-resin lexudates are obtained which haveas lowas 1% aqueous emulsifying medium when brine ls.used to increasethe specific gravitysof the water used in excess oi that required foremulsliication. Water which may bel associated with the emulsions inexcess of approximately 1% may notV be a part of the emulsion but may bemixed with the emulsion in the form of drops or larger globules.

y The use of brine is desirable as a means of reducing to a minimum theamount oi' aqueous medium held by the emulsion in the form of drops andlarger globules. The removal of such water is desirable to lessenshipping weights, to lessen the amount of water ultimately removed bydistillation, and to secure a more complete removal of water-solubleconstituents of the crude oleoresin. The electrolytic properties ofbrine are also useful in facilitating the removal of colloidal solids,which action of brine is more fully discussed below.

While it may be a primary object of emulsification to obtain stableemulsified oleo-resinous products, the stability of the emulsions is notessential to the purposeof purification or fractionation of the crudeoleo-resinous aggregate. In the latter instances, stability of emulsionsfor a, period of time sufficient to. meet the requirements of gravitysedimentation is satisfactory. The highly stable emulsified products areespecially desirable to meet the requirements of bulk storage andshipment between the initial preparation of the emulsions and theirultimate utilization.

The use of turpentine or the like in conjunction with emulsiiication isprimarily for the purpose of accentuating the difference in the specificgravity of the emulsiiied materials. Turpentine, itself, does notreadily emulsify with aqueous solutions until its viscosity is increasedby the solution of resinous materials; when this occurs., however, thesolutions emulsify readily. Its use, therefore, associates with theoperation of emulsiflcation the action of a selective solvent as well asa means of aecentuating differences in specific gravity. The viscousliquid constituents of crude oleo-resin enter into solution withturpentine liquefaction or emulsiiication of' the crystalline acids. Inview of the general requirements of operating practicability, however,the emulsiflcation process with the use of heat is preferred as a meansoi obtaining a progressive transition of the crude oleo-resin aggregateinto a state of high iiuidity. Finely divided fluid emulsions areadaptable to filtration so as to obtain an effective separation of theemulsiiied materials from 'the solid impurities ordinarily present inthe crude oleo-resin aggregate. A condition of high fluidity alsoaccelerates gravity sedimentation.

An important'feature of the present invention is the separation from theoleo-resins of the materials of group 4 listed above, including thecolloidal suspensions such as dust, pollens and other finely dividedforeign matter. These finely divided solids which ordinarily remainin.suspen sion in liquefied oleo-resin even after long periods ofsedimentation, have greatly contributed to the difficulty of effectivefiltration of liquefied oleoresin. Their removal by means of filtrationhave required iiltering media of relatively high density such as paper,felts and similar materials. Such media require high filteringpressures, extremely low vi:coslties, usually obtained with solvents andhigh temperatures, and Irelatively frequent replacement of the filteringmedia. All of these requirements mitigate against economical filtrationto the degree of making the use of such media impractical from acommercial viewpoint. I have discovered, that after thoroughemulsification with brine or the like these finely divided solids nolonger remain in suspension but instead, settle out of the filteredemulsions along with the brine introduced in excess of that required foremulsication. They collect on the surface of the settled brine in agrayish foamy stratum which is removed together with the settled brine.This foamy stratum also contains some of the highest gravity emulsiedoleo-resinous products. It is believed that this sedimentation is aninstance of colloidal suspension being relieved by theuse of anelectrolyte. The importance of the sedimentation from the practicalviewpoint is that it eliminates the necessity of removing these finelydivided solid impurities by means of a filtering medium. If a filteringmedium is used it may be of relatively high porosity, permitting highrates of filtration with low filtering pressures, relatively lowtemperatures and with yviscosities readily obtained without the use of asolvent. In fact, the preferred porosity of the filtering media used inmy process is one that permits'the finely divided globules composing theemulsions to pass through it. A loosely woven, iight-weight, Cantoniiannel has proved to be a satisfactory filtering medium.

Processing crude pine oleo-resin exudates by means of initiallyconverting the exudates into finely divided iiuid emulsions, whichemulsions are temporarily kept suspended in an aqueous electrolyte ofhigher specific gravity than the emulsiiied materials, greatlyfacilitates the removal of solid impurities by means of filtration, inthat it relieves the filtering medium from the duty of retainingcolloidal and semi-colloidal solid materials. Such materials are carriedout by the sedimentation of the electrolyte from the emulsiiiedoleo-resin exudates. The nature of this sedimentation will be more fullydiscussed in connection with a description of apparatus in which myprocess can be economically carried out. The apparatus is shown by wayof illustration in the accompanying drawing, in which:

Fig. 1 is a vertical sectional view partly in elevation of theapparatus; and Fig. 2 is a cross 'sectional view of a modified portionof the apparatus shown in Fig. 1.

The process of the present invention may be described by explainingthe-operation of the apparatus. Features of the apparatus are describedin detail in a copending application Serial No. 20,836, filed May l0,1935.

Oleo-resinous material to be treated, particularly crude oleo-resinousmaterial obtained. from trees in the manner set forth above, is placedin a. hopper I positioned abovea vessel 2 provided with a removablefilter head 3, and a removable screen 4 supportedl horizontally andcentrally by a concentrically arranged iixed screen 5 :at an upper levelwithin the vessel 2. In charging the vessel 2, the filter head 3 isremoved, the screen l is lifted out, and the valve 6 in the bottom ofthe hopper I is raised by pulling upwardly on the handle 1. .The bottomof the hopper I is conical in shape and is kept warm by a steam jacket 8so that the viscous aggregate will ow quickly from the'hopper into thevessel 2. It is not desirable to melt any substantial portion of thecharge while in the hopper since it is preferable that the melting bedone in the vessel 2 in the special manner described below. Asatisfactory batch of crude oleo-resins for treatment in the vessel 2 isfrom about eight to ten barrels. A ten barrel batch weighs approximately4,350 pounds. After the hopper I has been emptied, a new batch ofoleo-resinous material is introduced into it in order that a new chargemay be immediately available when the vessel 2 Vis ready to receive it.

The illter head 3 is of any desirable construction but preferably of thetype shown and described in my co-pending application Serial No. 20,836.Duplicate lter headsA 3 and 3 are provided one on each end of a leversupported at its midway point on a post Ill so that both filter headsare balanced. The support for the lever 9, constructed as shown in theabove application, permits of raising the filter head 3 up oif the mouthof the vessel 2 and of rotating it :about the post I0.

In the drawing the filter head 3' is shown hung by means of a chain IIin an inverted position to permit of cleaning it while the other lterhead 3 is in use. The normal position of the lter head 3 is shown indotted lines.

After the vessel 2 has been charged, the screen 4 is replaced, and thefilter head 3, fully assembled for filtration, is securely clamped onthe vessel 2. The filter head 3 is connected to a ilexible pipeconnection I2 and the valve I3 is closed. The vessel 2 is then a vaportight container lled with oleo-resin aggregate to a level preferablysubstantially below the level of the flange at the mouth of the vessel 2to which the lter head is attached. For a ten barrel batch it isdesirable to have an unfilled space in the vessel 2 between the upperlevel of the charge and the filter head of approximately gallons, toallow for expansion during heating. l

The vessel 2 is provided with a heating jacket I4 having inlet andoutlet means I5 and 'I6 respectively for a fluid heating medium. 'I'hevessel 2 is also equipped with a pressure steam jet, generallydesignated by the numeral I1. The batch of oleo-resinous material may bemelted, therefore, by means of indirect heat from the heating jacket I4o'r by injecting live steam directly into the oleo-resinous material.Superheated or saturated steam may be introduced.

It is desirable that substantially all of the melting be accomplished bythe injection of pressure steam in which case the steam moves at highvelocity at the time it contacts the oleo-resinl aggregate which is at alower temperature than the steam. The initial action resulting fromcontacting high velocity steam with crude oleo-resins of lowertemperature than the steam, is to form highly stable emulsions in whichthe aqueous dium is the dispersedphase, secondary emulsionsV are formedin which the primary emulsions of oleo-resinous material become thedispersed phase of the secondary emulsions. These secondary emulsionsare much less stable than the primary emulsions and their stability maybe modified by regulating the relative specic gravity of the aqueous andthe oleo-resinous components of the secondary emulsions.

Steam for emulsifying the oleo-resinous material is fed through a pipeI8 (having a valve IB) connected to a pipe I9 which in turn is connectedto a jet 20 adjacent the bottom of the vessel 2. By way of example,approximately 70 pounds of injected steam may be used per barrel ofcrude oleo-resin to convert the oleo-resin into a mixture of primary andsecondary emulsions heated to a temperature of approximately F. Thestable primary emulsions in which the aqueous medium is the dispersedphase, retain substantially one percent of their weight of suchdispersed aqueous medium. If the average water content of a barrel ofcrude oleo-resin before treatment is approximately 3l pounds, theapproximate condition of a batch of crude oleoresin contained in thevessel 2 after violent agitation thereof by injection of the steam andat the time the temperature has reached approximately 190 F. may bedetermined. 'I'his condition may be visualized from the following table:

Pounds 1. Primary emulsions of various oleo-resinous constituents,reduced to emulsied form at their initial contact with high velocitysteam emulsication and melting having occurred substantiallysimultaneously 3,900 f 2. Aqueous phase of secondary emulsions in whichthe above primary emulsions are the dispersed phase 1,000

Obviously the materials in the above table and the condition of thecharge will vary greatly. Quantitatively the figures given above have nospecific significance. The highly stable primary emulsions may beregarded as compositions containing the oleo-resinous materials reducedto a finely divided globular condition and the secondary emulsion may beregarded as a suspension of these globules in an aqueous medium. Theglobules-differ from each other in their specific gravity according tothe variable specific gravities of the oleo-resinous substances whichthe globules contain. 'Ihe rate of settlement of the various globules inthe aqueous suspension medium varies with their specific gravity,l theglobules of higher specific gravity moving toward the bottom of thecharge and those of lower specific gravity moving toward the top of thecharge.

When agitation ceases in the vessel 2, the conditions for stratificationof emulsied oleo-resinous materials through gravity sedimentation havebeen established. The relativespecic grav- :ity ofthe primary emulsionsand the aqueous phase of the secondary emulsion, which aqueous.

phase may be regarded as a fluid suspension medium for the-primaryemulsions, determines the period of time during Which-sedimentationoccurs. It is desirable to secure a substantially complete separation ofthe aqueous suspension medium of the secondary emulsion because it isthis medium, which, during the period of timev it is in intimate surfacecontact with the primary emulsions, acts as avselective solvent forwater-soluble acids and other water-soluble materials contained in thecrude oleo-resin aggregate. Atl the same time, however, its removal mustnot be accomplished so quickly as to substantially mitigate against itsfunctions as a selective solvent and as a fluid suspension mediumserving to accomplish a stratification of the stable primary emulsions.I have found that a substantially complete separation of the aqueoussuspen-f sion medium may be obtained in a sedimentation period ofapproximately ten hours duration by adding approximately two pounds ofsodium chloride per barrel of crudeoleo-resin composing the batch beingprocessed. The period of sedimentation can be shortened by increasingthe amount of salt added, or lengthened by decreasing the amount. Thesalt may be introduced into the melter in crystalline or solid form atthe time it is charged with crude oleo-resin or it may be introduced inthe form of a concentrated solution through a pipe 2| prior to or whileemulsification is in progress.

It has been previously stated that turpentine may be injected duringemulsification in order to accentuate the difference in specific gravityof the primary emulsions produced from the crude oleo-resin aggregate.'I'he turpentine to be thus added is introduced through a pipe 22 havinga valve 22 into a tank 23 equipped with a slight gauge glass 24.Compressed air is admitted through a pipe 25 having a valve 25' to thetank 23 and the rate of injecting the turpentine into the vessel 2, asemulsication progresses, is regulated by means of a valve 26, in case itis injected with the steam in the pipe I9 or by a valve 21 in case it isinjected through pipe 2|. I have'found that, generally speaking,satisfactory results may be obtained without the injection ofturpentine. In connection with the emulsication of oleo-resinousaggregates containing relatively large proportions of semi-solidifiedVoleo-resins, ordinarily called scrape, the injection of turpentine issometimes of sufficient advantage to warrant its use.

When the temperature of the emulsified oleoresinous aggregate reachesapproximately 190 degrees Fahrenheit, namely, a temperature, al

relatively small number of degrees below the boiling point of theemulsion, the injection of A steam is stopped and the period ofsedimentation begins. The trash, bark, pine needles, etc. quickalongwith the floating trash. While this sedimentation is in progress, valveI3 and the desired header valve 32 are opened and filtration is startedby the injection of high gravity brine into the bottom of vessel 2through pipe 2|. Instead of brine or sodium chloride solution, calciumchloride solution may be used. The solution may be that of any stablesalt or other compound that has a high specific gravity, is freelysoluble in water, and substantially or entirely inert with respect tooleo-resins.

The brine used as a liquid piston to force the emulsed oleo-resinousproducts in an upward direction toward the filter head 3, hasa specificgravity of approximately 1.15 and is supplied by a pressure pump 28. Thebrine passes through a meter 29 so that the amount injected into thevessel 2, and the rate of injection may be observed. A lpressure gauge30 connected to the brine line 2| at any convenient point between themeter 29 and the vessel 2, indicates the hydrostatic pressure generatedwithin the vessel due to the injection of the brine and the resistanceof the lteringmedium to the paage of the emulsied oleo-resins throughsaid filtering medium. Satisfactory filtration can be obtained byemploying pressures as high as 50 pounds or more per square inch. Theuse of lower pressures (about to 20 pounds per square inch) results inbetter operation.

As indicated above the preferable filtering medium is one having aporosity which permits the finely divided emulsions to pass through it.A light weight Canton fiannel or a free flowing, wire filter cloth areexcellently adapted for the filtration of the emulsions. The preferredrate of ltration is one which requires` from fortyve minutes to an hourto ll the vessel 2 with the high gravity brine. During this period offiltration the high gravity emulsified oleo-resin- `ous materials havesettled to the surface of the high density brine; a large proportion ofthe` aqueous phase of the secondary emulsions has .also settled, and,has become mixed with the high gravity brine producing a dilution of thehigh gravity brine by diffusion through the contact surface. The settledoleo-resinous emulsion thus becomes mixed with or suspended in the topstratum of the liquid piston.

The injection of the highv gravity brine is stopped when the meter 29indicates that the total gallons of brine injected equals the capacity,in gallons, of the vessel 2. At this stage of thefoperation some of thesettled emulsified oleo-resins together with the floating trashcontained in the charge are held beneath screen 3| in the filter head 3.

In commercial practice the flexible pipe connection I2 is connected to aheader containing several valves 32. Pipes 33 running from the headerconnect with several units comprising separators 34 and storage tanks35. At any stage of the filtering operation it is possible, therefore,to divert the filtrate into different tanks so that emulsions ofdifferent specific gravities are separately collected. The highestgravity emulsions are always diverted into a separate tank at the finalstages of filtration by injecting brine linto the vessel 2 in excess ofthe amount of brine required to ll the vessel. 'I'he heavy gummymaterials are tacky and tend to adhere to the floating trash and arelatively small quantity of highsolids are retained on a screen 31 in achamber 33; and the liquid aggregate flows back to a brine storage tankthrough a channel 39 and a series of cooling vats (not shown). As thedensity of the collected brine is increased by cool- 1 ing, emulsifiedoleo-resinous material and various gummy substances separate from thebrine in the form of scum which oats on the surface and is removedtherefrom. Solid matter collected on the screen 31 is removed therefromfor sedimentation in separator 34 is much longer than in the vessel 2;the separator is preferably so proportioned that material passingthrough it is retained in the separator for eight or nine hours, duringwhich time further stratification of the oleo-resin emulsion occurs. Theheavier emulsions accumulate in the separator 34 and the lighteremulsions flow through the separator into the storage tank 35 through apipe 43y and a valve 44. The heavier emulsions which accumulate in theseparator 34 may be periodically Withdrawn from the separator throughv asump 45. Aqueous solutions also settle in separator 34 and on thesurface of these aqueous solutions oats a frothy scummy sediment whichmay be separately collected and processed. The aqueous sediment isslightly saline 'due to the salt added during emulsication in the vessel2. The aqueous sediment and the scummy sediment are always removed fromthe separator 34 prior to the periodic removal of the heavier oleo-resinemulsions which gradually accumulate in the separator. y

'I'he aqueous sediment separated from the stable primary emulsions ofoleo-resin contains in solution three classes of material originallypresent in the crude oleo-resin aggregate, namely,

1. Water-soluble acids which are responsible for the corrosiveproperties of crude oleo-resin with reference to various metals.

2. Metallic salts of the above acids produced from contact of the crudeoleo-resin with metallic cups and gutters used for its collection. Whenthe aqueous sediment is treated with a caustic soda solution the variousmetallic hydroxides are thrown out of solution as a occulentprecipitate. These metallic salts are `highly undesirable adulterants ofcommercial gum rosins.

3. Organic water-soluble materials. These materials producea deep redcolor when the aqueous sediment is treated with caustic soda. This colorappears along with the precipitations mentioned above. When the redaqueous solution is separated from the precipitates by filtration andtreated with sulphuric acid, another precipitation occurs. After thisprecipitate forms the aqueous solution becomes colorless. Thesematerials are latent color bodies ordinarily present in gum rosins whichare responsible for the red color of rosin soaps.

The amount of precipitations obtained from the aqueous sedimentresulting from my process shows the efficacy of my process as a means ofremoving water-soluble adulterants `of crude pine oleo-resins. Thegravity stratification of the oleo-resin emulsions serves as a highlyuseful means of fractionating the crude pine oleoresin aggregates intodifferent classes of puried oleo-resins. Such fractionation has not beenpossible where the crude aggregates have been liquefied by methods whichreduce the crude aggregates to solutions.

The following determination of water contents in three typical batchesof crude oleo-resin being processed illustrate the degree ofsedimentation that occurs in the vessel 2, and in the separator 34:

'I'hese determinations indicate the relatively large amount ofsedimentation which occurs in the vessel 2 during the period of timedevoted to filtration. It is in the ltration stage of the operation thathighly oxidized oleo-resinous materials are removed. These materials arerelatively high in specificgravity and are relatively less soluble thanthe bulk of the oleo-resinous material. As indicated above some of theoxidized or gummy materials are deposited on the oating trash in thevessel 2.v These materials are also found mixed with the diluted surfaceof the liquid piston (brine) in the vessel 2. After removal of theoxidized materials from the vessel 2 through the valve 36, along withthe trash and the brine, and before recirculation of the brine in theprocess, such oxidized materials may be separated and collected andeventually distilled to produce low grade rosins such as grades B, D andE.

Most of the water-soluble impurities are removed before the emulsionsreach the separator 34. The aqueous sedimentation in the vessel 2dilutes the circulating stock of high gravity brine and graduallycharges it with water-soluble im- Y purities. This dilution of the highgravity brine requires periodic additions of salt to maintain its specicgravity and finally results in having to replace the adulterated brinewith fresh brine in order to avoid undesirable accumulations of metallicsalts and water-soluble hydrocarbons or other compounds in the highgravity brine. It has been more economical to renew the brine than toprocess it for the removal of metallic salts and hydrocarbons.

The sedimentation which occurs in the separator 34 is very importantalthough it is relatively small in quantity. The, aqueous sediment whichis removed ,from the separator is highly charged with impurities and thefoamy scum removed with it contains highly undesirable impurities.

All of the aqueous content of the emulsions which pass into the storagetank 35 is not embodied in the stable primary emulsions. Additionalwater not in the dispersed phase may separate in the storage tank 35 andcollect in a sump 46 from which it may be withdrawn by means of a drain41 provided with a valve 48.

'I'he vessel 2 and the separator 34 are preferably lagged to minimizeheat losses so that the emulsions will remain very uid during the periodof sedimentation. If desired a heating coil 49 may be provided in theseparator 34. Also, a heating means 50 may be provided in the storagetank 35 to make possible a more rapid v removal of the oleo-resinproduct through an outlet I which leads to tank cars or othercontainers. Material from the storage tank 35 may also be withdrawnthrough pipes 52 and 53 connected to the sump 46' which may be steamjacketted. 'I'he pipes 52 and 53 may lead to stills or other means forconvertinggthe oleo-resin into rosin and turpentine, paper size, orother commodity. A pipev 54 connected to the'top of the storage tank 35serves as a vent.

In order that an operator may separate a given batch into variousfractions and direct a fraction to the separator provided for it, a testvalve 60 above the header to which the exible pipe I2 is connected, maybe opened from time to time to obtain a sample of the material flowingfrom the vessel 2 during iiltration. An experienced operator can readilytell, from the color and general nature of a sample, at approximatelywhat point the passage of the filtered material to a given separator isto be cut of! and directed to another separator.

Any materials of lower speciilc gravity than the fraction of oleo-resinscollected in a given separator, when such materials are found floatingin the separator, may be removedthrough an outlet pipe 6| provided witha valve 6,2Y and a sight glass 63.

My process results in the accumulation, in each ofthe storage tanks 35of the apparatus described, of highly stable emulsions of pine oleoresinfrom which impurities, with which the oleoresinous material wascontaminated when it was a constituent of the crude oleo-resinaggregate,have' been removed. These emulsions remain homogeneous and fluid overlong periods of time, without any substantial recrystallization of resinacids. They are substantially non-corrosive to metals and are generallyadapted to storage in bulk and to transportation in tank cars or othercontainers. 'I'hese emulsions are so stable that they can `not be brokenexcept by active boiling such as occurs in distillation. The stabilityof the oleo-resin emulsions is associated with a inely dispersed aqueousliquid phase. It is believed that the highly ionized water-soluble acidspresent in crude oleo-resin are eiective emulsifying agents forproducing the stable primary oleo-resin-water emulsions, with theaqueous solution of the acids as the dispersed phase. In this phase theacid solution is protected from dilution by the aqueous phase of thesecondary emulsions in which the primary emulsions are suspended. Afterthe aqueous phase of the secondary emulsions has been removed bysedimentation the dispersed, aqueous phase of the vprimary emulsionsdoes not come in contact with the metal containers which kmay be usedfor the storage and shipment of the stable' primary emulsions. Thedispersed aqueous .phase of the stable emulsions, therefore, does noteffect corrosion even though it does contain some of the acids Which arecorrosive when in direct contact Awith metal.

My method of emulsifying the crude oleo-resinous aggregate by means ofhigh pressure steam injected into cold crude oleo-resin aggregate ispeculiarlyadapted to the initial formation of the primary emulsions andto the subsequent formation of the secondary emulsions having avoluminous water phase in intimate surface contact with the finelydivided globules of the stable emulsions.

' Similar two stage emulsif'lcation can be produced 'by means ofmechanical agitators but my steam jet method is much more effective andeconomical. It is especially effective in the formation of moving athigh velocity, contacts the cooler oleo-` resin condensation and meltingoccur simultaneously. The dispersed initial condensation makes contactwith the water-soluble acids dispersed through the crude oleo-resinousaggregate and thus forms the dispersed phase of the stable primaryemulsions.

With hot emulsification the aggregate amount of the dispersed liquidphase is small, not generally exceeding about one percent of the Weightof the stable emulsions of which it is a part. The quantity of acid,therefore, contained in this liquid phase is only a small proportion ofthe total water-soluble acids originally present in the crudeoleo-resin. The great proportion of these acids is dissolved in theexternal aqueous phase of the secondary emulsion and is removed withthis aqueous phase after sedimentation. This is likewise true withrespect to other water-soluble materials present in the crude oleo-resinaggregate. The water solution, which is removed during the period ofsedimentation, contains the highly corrosive acids which were present inthe crude oleo-resin, the salt added to increase the specific gravity ofthe solution, and other Watersoluble materials present in the crudeoleo-resin. This aqueous solution is highly corrosive to metals. Thesmall traces of acid substances which remain dispersed in the stableprimary emulsions .have substantially no corrosive action on account oftheir dispersion. The corrosive properties of the separated aqueoussolution become particularly noticeable in thebottom part of the vessel2 and separator 34 and, to a less degree, in the bottom parts of thestorage tanks 35. The drainage sumps are particularly subjected to thecorrosive action of the aqueous sediment. The corrosive acids alsoaccumulate in the high gravity brine used as a liquid piston in theltration apparatus and in this instance affect the durability ofscreens, pumps, and other metal equipment with which the high gravitybrine comes into contact.

In copending applications Serial No. 34,623, filed August 3, 1935, andSerial No. 24,981, led June 4, 1935, I have described a method ofintroducing alkaline agents in vessel 2 during the process ofemulsifying the crude oleo-resin exudates. Such use of alkali serves toprotect plant equipment from the corrosive action of the aqueoussolutions. Another highly effective means of eliminating corrosion inplan equipment is to use suitable metals which are resistant to thecorrosive acids contained in the aqueous solutions. By using suchmetalsthe general formation of rust incident to the use of mild steelequipment is also eliminated. On this account it is preferable to useresistant alloys in plant equipment, and when such alloys are used it isnot at all necessary to resort to the methods of the above mentionedapplications. It is to be understood that the main purposes of theaqueous suspension medium are,

1. To act as a selective solvent for the various Water-soluble materialscontained` in the crude oleo-resin exudates being processed and by thesolution of such materials to accomplish their removal from the stableemulsions when the aqueous medium is removed from the emulsions by meansof gravity sedimentation. These purposes are` best served by maintainingthe acidity of the aqueous suspension medium until it is re- A moved bysedimentation in separator 34. Neutralization of acidity in vessel 2, isa modification of the process which adapts it for use with cqu'pmentconstructed of mild steel.

2. To act as a fluid suspension medium for the oleo-resin emulsions soas to permit these emulsions to arrange themselves freely according tothe relative specific gravity of the globules composing the emulsions.This purpose is best served by simultaneous melting and emulsication soas to avoid the formation of solutions of various constituents of thecrude aggregate with each other.

l 3. To serve as a medium for collecting colloidal and semi-colloidalsolids which are present in the crude oleo-resin exudates and carryingthese solids with it as it settles from the oleo-resin emulsions. Thisis 4of primary importance as an aid lto filtration. In fact. thisprinciple of removing nely divided solids is, apparently, a vitalelement in the economic filtration of crude pine oleo-resin exudates.

All of the above three functions of the medium described are functionsof the secondary emulsions formed withD the higher gravity aqueousmedium and they depend upon the fact that these y secondary emulsionsare only moderately stable. 'I'he initial formation of the highly stableoleoresin emulsions in which an acid aqueous medium is a dispersed phasehas no relation to accomplishing the objectives enumerated above but ithas been discovered that it is this type of emulsiflcation whichproduces an oleo-resin product that remains homogeneous in its structurethrough a sufliciently long period of time to meet the requirements ofbulk transportation and storage of the commodity prior to its intimateuse by consuming industries.

It .will be observed from the foregoing description and data that thesecondary emulsions separate at a variable rate. The initial separationof the aqueous medium is at a comparatively rapid rate and occurs in thevessel 2. In two examples cited approximately of the aqueous medium*separated from the secondary emulsion in the vessel 2, While in anotherexample 4cited approximately of the aqueous medium separated from theemulsion in the vessel 2. It is obvious that the percentage of thisaqueous medium which separates in the vessel 2 is a function of thespecific gravity of the aqueous medium and of the period of time thesecondary emulsions are held in the vessel 2. The control of both'ofthese variables is a part of the operating technique of my process,which may readily be adjusted to obtain an observed perfomance. Theseparation which occurs in the vessel 2 is of greatest aid to ltrationand if necessary the charge may be retained in the vessel 2 until aftersubstantially all of the aqueous medium has separated from the secondaryemulsion. The fact, however, that ,l

the separation can be carried out in two distinct phases greatlyfacilitates the rapidity of the filtration.

A very high percentage of the total colloidal and semi-colloidalmaterials present in the crude oleo-resin aggregate is carried down bythe aqueous medium which separates in the vessel 2. It is the fact,however, that suchcolloidal material as may pass through the filteringmedium is later removed. by the continued sedimentation` of the aqueousmedium in the separator 34, that permits high rates of filtrationobtainable with a relatively porous and free-flowing filtering medium.Heretofore, efforts to filter pine oleo-resin exudates have dealt withsolutions of the exudates either obtained by means of heat or by meansof added solvents, or both of these means combincd. In such cases thecolloidal and semi-colloidal materials remained suspended in thesolutions and their removal had to be accomplished by the filteringmedium. Their removal in this manner necessitated filtering media ofrelatively high density and also high uidity of the oleoresins usuallyobtained with added solvents and hightemperatures, and also high lteringpressures. Rates of filtration were so low and operating costs so highthat the commercial ltration It may be said, with reference to the aboveviscosities, that emulsions having a viscosity of 60' are viscous fluidswhich readily flow through spouts 8 inches in'v diameter from elevatedstorage tanks into tank cars. An 8,000 gallon tank car can be filledwith such material in approxi- A mately one hour. Materials havingviscosities of approximately 5 minutes can be readily handled withpumps. Viscosities of less than 5 minutes indicate high degree ofliquidity. These data indicate that for pumping, my oleo-resin emulsionsshould be heated to at least 50' degrees C., or to 122 degreesFahrenheit.

The operations thus far described, result primarily in the production offiltered emulsions of pine oleo-resin exudates in which an acid aqueousmedium is the dispersed phase of the emulsion. This dispersed phaseaggregates approximately 1% of the weight of the emulsion. Suchemulsions have the stability to meet all of the requirements of bulktransportation and storage prior to their use for the production ofrosin and turpentine, or direct use for the production of soap, papersize or other products.

While the dispersed aqueous phase of these emulsions contains some ofthe corrosive acids originally present in the crude oleo-resin, thisdispersed phase does not come in contact with vessels which might beused for the storage and transportation of the products. It has beenpointed out previously, however, that all of the aqueous medium, inwhich the emulsions were suspended during their preparation, may not beseparated from the emulsions during the period of sedimentation. Theinstances cited are typical of good commercial plant operation. In theseinstances the separation of the aqueous suspension medium issubstantially complete. In commercial operations, however, overcrowdingof equipment is frequently necessary and emulsions incorporating thewater content of the oleo-resinv may be produced which contain largeramounts of the aqueous suspension mediumdispersed through the emulsionin the form .of droplets. As long as such droplets remain suspended inthe emulsion they have no corrosive action `on the metal containersexceptl where they contact the metal. Corrosion resulting from suchlimited contact is negligible. It the suspended aqeuous solution settlesout of the emulsion on long standing some corrosive action may belocalized at the bottom of mild'steel containers, since these aqueoussolutions are both mildly acid and saline. While, commercially, suchpossibilities oi corrosion are of little importance, means oi preventingit may be provided if such` suspended water is used in thek formation ofa soap solution. 'The acidity may thus-be neutralized a-nd the soapsolution may be advantageously incorporated as a stable ingredient ofthe emulsion.

Let it be assumed that it is desired to produce emulsions containing ashigh as 4% of the aque-4 ous suspension medium held suspended in theemulsions, or, to protect the emulsion against a possible aqueoussuspension of.` this amount. Let it be assumed also that it is desiredto incorporate this suspended water into a 10% soap solution,(approximately). 'I'he medium for producing the desired amount of soap,say, is a 10% solution of NaOH. One pound of such solution added to theoleo-resin would produce approximately 0.82 pound of resin soapsincorporated with .9 pound of water contained in the solution of NaOH.It' would require approximately 6.5 pounds additional Water to produce a10% soap solution and with 4 pounds of suspended water available per 100pounds of emulsion, it would require 160 pounds of emulsion to supplythe water required to produce a 10% soap solution.

vIt would therefore take 1 pound of 10% NaOH solution per 160 pounds ofemulsion to accomplish the desired result. The acidity of the aqueousmedium suspended in the emulsion would, of course, modify slightly theactual amount of resin soap produced by the added alkali since some ofthe alkali would be used in neutralizing the water soluble acids. Sample3, above, is an emulsion in which the suspended aqueous medium was fixedby its conversion into a 10% soap solution. It

vwill be seen that the soap solution has little elIect on the viscositytemperature relations of the emulsion. It has been observed, however,that emulsions processed in this way are very stable and are entirelyfree from corrosive action on metals. Aqueous solutions of other alkalisas well as ammonium hydroxide may be used as means of forming soapsolutions withinthe emulsions. Prepared solutions of resin soap may alsobe used instead of aqueous solutions of various alkalis.

The general procedure of calculating the amount of alkaline agentrequire to produce a desired soap solution is the same as that outlinedfor a 10% solution of NaOH. I'he alkaline agent must be introducedgradually while the oleo-resin aggregate is being effectively stirred oragitated so as to obtain a uniform production and distribution of thesoap solution throughout the oleo-resin aggregate. 'I'he operation offorming the soap solution is carried out most effectively when thetemperature of the oleo-resin is merely high enough to produce moderatefluidity.

Proper sedimentation in the process herein de-` scribed eliminates thedesirabilityoof introducing soap solutions as an ingredient of myoleo-resin emulsions. Producing non-corrosive and stably homogeneousoleo-resin aggregates by mleans of into a soap solution is primarilyapplicable to the treatment of small batches of oleo-resins nottributary to properly equipped processing plants. Crude oleo-resins ascollected from the forest contain approximately 8% of water entrapped inthe viscous aggregate. This water will vary through considerable limits.By melting the crude aggregate and straining the liqueiied material allextraneous trash except finely divided trash can be removed. Then bystirring in 1 pound oi 10% sodium hydroxide solution per 180 pounds ofliquefied oleo-resin the acid aqueous content of the oleo-resin isconverted into a soap solution, which incorporated with the oleo-resin,inhibits recrystallization of resin acids and makes the oleo-resinaggregate non-corrosive to metal containers. 'I'his is one simple methodwhich I have discovered for converting crude oleo-resin aggregates intoa non-corrosive, stably homogeneous commodity adapted for bulktransportation and storage.

In this discussion a 10% soap solution has been used merely as anexample and not as a definition of a signiiicant limit. Dilute soapsolutions, say 2% to 4% solutions, are good emulsifying agents forproducing emulsions of oleo-resin having continuous aqueous phases. Insuch emulsions the continuous aqueous phase aggregates approximately 25%of the weight of the emulsion.

By injecting a suitable alkaline medium into the vessel 2 within theperiod of time devoted to the emulsication oi' the batch of crudeoleo-resin, the corrosive acids can be neutralized before they aredischarged from the vessel 2. In fact it is highly desirable, from thestandpoint of equipment cost and depreciation, to neutralize thecorrosive acids after they have been dissociated from the crudeoleo-resin, and prior to their discharge from' the vessel 2. Suchneutralization prevents the accumulation of corrosiveacids in the highgravity brine. 'I'he neutralization may be accomplished in a mannerwhich maintains the high gravity brine in a state of slight alkalinity,a feature not heretofore practiced. This results in eiiectivelyinhibiting corrosive action of the brine on the metals with which itcomes in contact. 'Ihe corrosive action in the separator Il and storagetank is also inhibited. Another important result incident to theneutralization of the aqueous suspension medium is, that -when thismedium is alkaline its association with the stable oleo-resin emulsionseliminates the chances of securing corrosive emulsions due to anypossible ineil'ective separation of the aqueous suspension medium fromthe emulsions during the period of sedimentation. y

The hydroxides of the alkaline earth metals such as calcium, barium,strontium, or magnesium are the most suitable alkaline agents to use,since they react readily with the highly ionized water-soluble acids butdo not react appreciably with the resin acids under the temperatureconditions associated with emulsication and ltration. This selectiveactivity oi' these alkaline materials permits their use without regardto the possible effect of them upon the resin acids. They may beintroduced into the vessel 2 in amounts greater than necessary toneutralize the water-.soluble acids without the .production ofwater-soluble resinates, which would occur with excess amounts ofhydroxides of the alkali metals. The hydroxides and carbonates of thealkali metals such as sodium and potassium can be used but their use isassociated with the necessity of uol determining with approximateaccuracy the amount of water-soluble acids present in the crudeoleo-resins being processed.

The quantity of water-soluble acids present in crude pine oleo-resinsmay be determined by separating all of the volatile constituents of theoleo-resin by means of steam distillation in a manner that retains allof the aqueous distillate. The acidity of this aqueous distillate .isthen determined by means of ordinary methods of titration. Generally theamount of water-soluble acids contained in an average barrel of crudeoleo-resin require for their neutralization approximately 11 grams oiNaOH, or approximately 10 grams of Ca(OI-I)z. If a saturated cold watersolution of Ca(OH)z is being used for neutralization, about 11/2 gallonsof solution per barrel (435 pounds) of crude oleo-resin being processedwould have to be injected. Effective results, however, can be obtainedby injecting Ca(OH)2 in the form of milk of lime. For reasons givenabove, Ca(OH)2 is the preferable alkaline reagent to use and it is usedin appreciable excess quantities to that required for the theoreticalneutralization of the water-soluble acids since the amount ofwater-soluble acids present in crude oleo-resin vary in diierent classesof crude. In commercial practice sumcient Ca(OH),z is injected into thevessel 2 to maintain the high gravity brine, used as a liquid piston inthe filtration operation, in a state of slight alkalinity.

The alkaline solution to be injected intothe vessel 2 passes through apipe 10 having a valve 1I, into a tank 12 provided with a gauge glass13. Compressed air is passed into the top of the tank 12 through a pipe14 having a valve 15.

The volume of alkaline solution forced 'from the tank 12 is indicated bythe change in liquid level in the tank as shown by the gauge glass 13.By means of outlet valves 16 and 11, the alkaline solution may beinjected into the vessel 2 through the pipe i9 and jet 20 together withthe high velocity steam supplied by the pipe i8 pr, it may be injectedthrough the pipe 2l.

l In the modified injection means shown in Fig. 2, the pipe 2| providedwith a valve 12| is connected to a side of a nozzle 18 which may besubstituted for the injecting nozzle shown in Fig. 1. The alkalinereagent fedthrough a pipe 19 having a valve 80 that is connected to thetank 12 mixes in the injecting means 2li with the steam fed by the pipeI9 having a valve I9.

The alkaline solution may be gradually. admittedthroughout the period ofmelting and emulsiflcation, in which case the Water-soluble acids areneutralized as rapidly as they are dissociatedv from the crudeoleo-resin, 4or the alkaline solution may be admitted in the last stagesof the melting and emulsifleation operation. This latter method ofinjecting the alkaline solution is preferable because the solvent actionof the aqueous suspension medium is increased by its acidity.

maintaining the acidity of the aqueous suspension medium until it isremoved by sedimentation in the separator 34. Neutralization of thissuspension medium in the vessel 2 in the manner just described, ispresented as a modiication l which adapts the process to the use ofequipment constructed of mild steel or aluminum for instance instead ofmore expensive metals such as stainless steel which may be moreresistant to the corrosive properties of the said aqueous soluil tionremoved by sedimentation.

When the aqueous suspension medium isneutralized in the vessel 2, in themanner described above, precipitates are formedand these precipitatessettle in the vessel 2 while filtration is in 1,

progress and are finally discharged from the vessel along with the highgravity brine and solids removed by iiltration. These precipitates areof such high specific gravity that they settle in the high gravity brineand after sedimentation 2 preferably contain no crystals orsubstantially 3 no crystals of resin acids and as indicated aboverecrystallization of such acids, after melting and emulsiiication of theoleo-resin exudates, is inhibited.

The present application is a continuation in g part of applicationSerial No. 20,836, iiled May 10, 1935, and of application Serial No.34,623 filed August 3, 1935, and of application Serial No. 24,981 ledJune 4, 1935.

I claim: 4

1. A method comprising mixing together water and crude oleo-resinexudate to prepare a relatively unstable emulsion lcontaining acontinuous water phase and globules of a relatively stable emulsionhaving a dispersed phase cond taining water and a continuous phasecontaining oleo-resinous exudates obtainedI from pine trees, removingparticles of waste matter contained in the oleo-resinous aggregate, andseparating the said relatively stable emulsion from 5 the saidcontinuous water phase of the said relatively unstable emulsion.

2. A method comprising mixing together water and oleo-resin exudate toprepare a relatively unstable emulsion containing a continuous wai terphase and globules of a relatively stable emulsion having a dispersedphase containing water and a continuous phase containing oleo-resinousexudates obtained from pine trees, removing solid waste matter,water-soluble matter, and modie lied terpenes and modified resin acidscontained in the oleo-resinous aggregate, and separating the saidrelatively stable emulsion from the said continuous Water phase of thesaid relatively unstable emulsion. e

3. A method comprising mixing water and oleoresinous exudates obtainedfrom pine trees to form an emulsion, discontinuing the mixing andcausing the resulting mixture to separate by sedimentation into aplurality of fractions contain- 7 ing emulsions of different specicgravities, and separately collecting the said fractions.

4. A method comprising mixing water and oleoresinous exudates obtainedfrom pine trees to form an emulsion, discontinuing the mixing and 7 Theresult of 2 causing the resulting mixture to separate bysedimentationinto a plurality of fractions containing emulsions of different speclncgravities. separating from `the resulting stratiiled material solidwaste matter, water-soluble matter, and modiiled terpenes and modiiledresin acids contained in the oleo-resinous aggregate, and separatelycollecting the said fractions.

5. A method comprising mixing water and oleoresinous exudates obtainedfrom pine trees to form an emulsion, which emulsion contains a mixtureof oleo-resinous emulsions of different specinc gravities, addingturpentine to accentuate the differences in specific gravities of thesaid emulsions, causing the resulting mixture to separate bysedimentation intaa plurality of fractions, and separately collectingthe said fractions.

'6. In a method of treating oleo-resinous exu dates obtained from pinetrees, mixing the said oleo-resinous exudates and an aqueous mediumsubstantially inert with respect to the said exudates and of higherspecific gravity than the oleo-resinous aggregate of the said exudatesto form a relatively unstable emulsion containing the said aqueousmedium in a continuous aque-i ous phase, and a dispersed phasecontaining a relatively stable emulsion of the oleo-resinous aggregateand the said aqueous medium. and eifectlng a separation of therelatively stable emulsion from the said continuous aqueous phase.

7. In a method of treating oleo-resinous exudates obtained from pinetrees, mixing the said oleo-resinous exudates and brine to form arelatively unstable emulsion containing a continuous brine phase and adispersed phase containing a relatively stable emulsion of theoleoresinous aggregate and. brine, and eifecting a separation of brineand the relatively stable emulsion.

8. In ay method of treating oleo-resinous exudates obtained from pinetrees, mixing the said oleo-resinous exudates and water to form anemulsion and to dissolve in the water the water-l soluble acidscontained in the said oleo-resinous exudates, mixing an alkaline agentwith the emulsion to reduce the acidity of the said waters'oluble acids,and separating emulsiiied oleo-resinous aggregate from the resultingmass.

9. In a method of treating oleo-resinousv exudates obtained from pinetrees, mixing the said oleo-resinous exudates and water to form anemulsion and to dissolve in the water the watersoluble acids containedin the said oleo-resinous exudates, and while effecting emulsiilcationadding an alkaline agent to combine with watersoluble acids in thewater, and separating emulsied oleo-resinous ,aggregate from theresulting mass.

10. In a method of treating oleo-resinous exudates obtained from pinetrees, mixing the said oleo-resinous exudates thoroughly with water toform an emulsion and to dissolve in the water the water-soluble acidscontained in the said oleoresinous exudates; and in ythe latter stagesof emulsiiication after obtaining an increase of acid concentration inthe water to effect the increased solvent action resultant of suchincrease of acid concentration. distributing an alkaline solutionthroughout the mixture to reduce the acidity o! the water,'and removingemulsifled uncombined oleo-resins from the resulting mass.

11. In a method of treating oleo-resinous exudates obtained from pinetrees, mixing the said oleo-resinous exudates and an aqueous mediumsubstantially inert with respect to the said exudates and of higherspeciiic gravity than the oleoresinous aggregate of the said exudates todissolve in said medium water-soluble acids contained in the saidoleo-resinous exudates, and during at least the latter portion of theperiod of mixing maintaining the said medium in alkaline condition butavoiding substantial conversion of resin acids into resinates to obtainan oleo-resin aggregate from which water-soluble acids have been removedand in which a major portion of the oleo-resins has been unaffected bythe alkalinity of the said aqueous medium.

12. *In a method of treating oleo-reslnous exudates obtained from pinetrees, mixing the said oleo-resinous exudates and an aqueous mediumsubstantially inert with respect to the said exudates and of highervspeciiic gravity than the oleoresinous aggregate of the said exudatesto dissolve in said medium water-soluble acids contained in the saidoleo-resinous exudates, and during at least the latter portion of theperiod of mixing, introducing a solution of alkaline earth hydroxide toreduce the acidity of the said aquev ous medium resulting from themixing operation but avoiding substantial formation of resin soaps, andseparating from the resulting mass oleo-resinous aggregate that has beenunchanged by the said hydroxide.

13. In a method of treating oleo-resinous exudates obtained from pinetrees, mixing the said oleo-resinous exudates and an aqueous mediumsubstantially inert with respect to the said exudates and of higherspecific gravity than the oleo-resinous aggregate of the said exudatesto dissolve in said medium water-soluble acids contained in the saidoleo-resinous exudates, and during at least the latter portion of theperiod of mixing introducing calcium hydroxide to reduce the acidity ofthe said aqueous medium resulting from the mixing operation but avoidingsubstantial formation of resin soaps. and separating from the resultingmass oleo-resinous aggregate that has been substantially unaffected bythe calcium hydroxide.

14. In a method of treating oleo-resinous exudates obtained from pinetrees. mixing the said oleo-reslnous exudates, an aqueous mediumsubstantially inert with respect to the said exudates and of higherspecific gravity than the oleo-resinous aggregate of the said exudates.and an aikaline agent to form an emulsion containing a continuousaqueous phase of slight alkalinity and a dispersed emulsion containingoleo-resins uncombined with the alkaline agent.

15. In a method of treating oleo-resinous exudates obtained from pinetrees, mixing the said oleo-resinous exudates, an aqueous mediumsubstantially inert with respect to the said exudates and of higherspecific gravity than the oleo-resinous aggregate oi the said exudates,and an alkaline earth hydroxide to form an emulsion containing acontinuous aqueous phase of slight alkalinity and a dispersed emulsioncontaining oleo-resins uncornbined with the said hydroxide.

16. In a method of treating oleo-resinous exudates obtained from pinetrees, mixing water and oleo-resinous exudates to form an emulsion,causing solid and semi-solid suspended matter to separate from theemulsion by settling, iiltering the emulsion, and separating water fromthe resulting emulsion to such an extent that the water. is no longerpresent in the oleo-resin product as a continuous phase.

17. In a method of treating oleo-resinous exudates obtained from pinetrees, mixing water and oleo-resinous exudates to form an emulsion,causing solid and semi-solid suspended matter to separate from theemulsion by settling, filtering the emulsion, and separating water fromthe resulting emulsion to such an extent that the water is no longerpresent in the oleo-resin product as a continuous phase, andincorporating excess Water remaining in the said oleo-resin product in aresin soap solution to obtain an oleo-resin aggregate containing arelatively small proportion of the said soap solution.

18. In a method of treating oleo-resinous exudates obtained from pinetrees, mixing the said oleo-resinous exudates, an aqueous medium inertwith respect to the said exudates and of higher specific gravity thanthe oleo-resinous aggregate of the said exudates, and an alkali resinsoap to form an emulsion containing oleo-resins and an aqueous phasecontaining the said soap.

19. A method comprising mixing water and oleo-resinous exudates obtainedfrom pine trees to form an emulsion but avoiding dissolution to anysubstantial extent of component parts of resinous constituents havingdifferent specific gravities, discontinuing the mixing and causing theresulting mixture to separate bysedlimentation into a plurality offractions containing resin constituents of different speciilc gravities,and separately collecting the said fractions.

20. In a method of treating oleo-resinous exudates obtained from pinetrees, mixing the said oleo-resinous exudates and Water to form anemulsion, causing the emulsion to stratify into fractions of differentspecic gravities filtering the emulsion to separate solid and semi-solidsuspended matter contained in the said exudates, and separating theltered exudates into fractions of different specic gravities.

21. A composition comprising a fluid emulsion consisting of an aqueousmedium and pine oleoresin exudate, the said aqueous medium beingdispersed in the exudate and substantially inert with respect to thesaid exudate, the said exudate containing a relatively small amount ofresinate material selected from a group consisting of alkali, ammoniumand alkaline earth resinates dispersed in uncombined resin acids andterpenes of the said exudate, and the said emulsion being non-corrosiveto metals.

22. A composition comprising a fluid emulsion consisting of an aqueousmedium and pine oleoresin exudate, the said aqueous medium beingdispersed in the exudate and substantially inert with respect t'o thesaid exudate, the said exudate containing a relatively small amount ofsodium resinate dispersed in uncombined resin acids and terpenes of thesaid exudate, and the said emulsion being non-corrosive to metals.

23. A composition comprising a'uid emulsion consisting of an. aqueousmedium and pine oleoresin exudate, the said aqueous medium beingdispersed in the exudate and substantially inert with respect to thesaid exudate, the said exudate containing a relatively small amount ofcalcium resinate dispersed in uncombined resin acids and terpenes of thesaid exudate, and the said emulsion being non-corrosive to metals.

24. A composition comprising a fluid emulsion consisting of an aqueousmedium and pine oleoresin exudate, the sai-d aqueous medium beingdispersed in the exudate and substantially inert with respect to thesaid exudate, the said exudate containing a relatively small amount ofammonium resinate dispersed in uncombined resin acids and terpenes ofthe said exudate, and the said emulsion being non-corrosive to metals.

25. A composition comprising a fluid emulsion consisting of brinedispersed in pine oleo-resin exudate, the said exudate containing arelatively small amount of resinate material selected from a groupconsisting of alkali, ammonium and alkaline earth resinates dispersed inuncombined resin acids and terpenes of the said exudate, and the saidemulsion being non-corrosive to metals.

26. An emulsied pine oleo-resin comprising an oleo-resin exudate in onecomponent of the emulsion, the said exudate consisting of constituentsof substantially all of the relatively waterinsoluble portion of pinesap as obtained from living trees including uncombined resin acids,terpenes and other oleaginous constituents normally contained in suchsap; and as another component a relatively small amount of an aqueousmedium substantially inert with respect to the said oleo-resin exudate,dispersed in the water-insoluble oleo-resin exudate, the said aqueousmedium including water other than the natural water content of the saidexudate and the said emulsion being substantially non-corrosive tometals and being a stable fluid product at temperatures below that atwhich active boiling of the said product occurs.

27. An emulsied pine oleo-resin comprising an oleo-resin exudate phaseand a dispersed aqueous phase, the said exudate phase consisting ofconstituents of substantially all of the relatively water-insolubleportion of the exudate as obtained from trees including resin acids,terpenes, and other oleaginous constituents normally contained in crudeexudate; the said dispersed aqueous phase including water other than thenatural Water content of the said exudate and acidiled by Water-solubleacids originally present in the crude exudate andthe said emulsifiedpine oleo-resin being substantially non-corrosive to metals and being astable uid product at temperatures below that at which active boiling ofsaid product occurs. t

28. A method comprising thoroughly mixing together an aqueous medium andcrude oleoresinous exudates obtained from pine trees and containingwater-soluble acids and relatively Water-insoluble constituentsincluding resin acids, terpenes, and other oleaginous compounds normallycontained in the said exudates, the said aqueous medium' beingsubstantially inert with respect to the said water-insolubleconstituents, dissolving water-soluble acids in the said aqueous mediumand thereby separating them from the said Water-insoluble constituents,and dispersing the latter to form a dispersion of a relatively stableemulsion having a dispersed component containing Water and a continuouscomponent containing the said Water-insoluble constituents.

MCGARVEY CLINE.

